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WO2017125358A1 - Procédé de production à catalyse homogène de pipérazines mono-n-substituées - Google Patents

Procédé de production à catalyse homogène de pipérazines mono-n-substituées Download PDF

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WO2017125358A1
WO2017125358A1 PCT/EP2017/050824 EP2017050824W WO2017125358A1 WO 2017125358 A1 WO2017125358 A1 WO 2017125358A1 EP 2017050824 W EP2017050824 W EP 2017050824W WO 2017125358 A1 WO2017125358 A1 WO 2017125358A1
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hydrogen
alkyl
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complex catalyst
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Simone WOECKEL
Marion DA SILVA
Mathias SCHELWIES
Hendrik De Winne
Michael Limbach
Ulrich Abel
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/04—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to a process for preparing mono-N-substituted-piperazines (I) by homogeneously catalyzed alcoholamination of alcohols (I I) with piperazine (II I) in the presence of a complex catalyst (IV) containing iridium.
  • Mono-N-substituted-piperazines are used, inter alia, as intermediates in the preparation of fuel additives, surfactants, pharmaceutical and plant protection agents, hardeners, for epoxy resins, catalysts for polyurethanes, intermediates for the preparation of quaternary ammonium compounds, plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile auxiliaries , Dyes, vulcanization accelerators and / or emulsifiers.
  • Mono-N-substituted-piperazines therefore represent a commercially extremely interesting class of substances that can be used in a wide variety of applications.
  • DE 2 531 060 describes a process for the simultaneous preparation of 1-methylpiperazine and 1, 4-dimethylpiperazine.
  • formaldehyde and piperazine are reacted in a liquid solvent in the presence of a supported hydrogenation catalyst.
  • a disadvantage of this process is that always mixtures of 1-methylpiperazine and 1, 4-dimethylpiperazine are obtained.
  • the 1, 4-dimethylpiperazine is usually produced in similar amounts as the 1-methylpiperazine. In some cases, the 1, 4-dimethylpiperazine even the main product of the reaction is.
  • With the method according to DE 2 531 060 can be produced only 1-methylpiperazine and 1, 4-dimethylpiperazine, always mixtures are obtained.
  • the economically interesting mono-N-substituted piperazines are not accessible in pure form by this process.
  • WO 2013/178693 describes a process for the preparation of mono-N-alkylpiperazines by reacting diethanolamines with a primary amine in the presence of hydrogen and a shaped catalyst body.
  • WO 2013/178534 also describes a process for the preparation of mono-N-alkyl-piperazines by reacting diethanolamine with a primary amine in the presence of hydrogen and a supported metal-containing catalyst. Even with the method according to WO 2013/178534, mono-N-alkyl-piperazines are made available in good yields and satisfactory selectivities.
  • a disadvantage of the method WO 2013/178534 is also the necessity of the presence of hydrogen and the implementation of the reaction at high absolute pressures in the range of 95 to 145 bar.
  • the process according to the invention is intended to make mono-N-substituted-piperazines (I) available in good yields and with good selectivities.
  • R 2 and R 3 are independently selected from the group consisting of hydrogen, unsubstituted or at least mono-substituted d-Cso-alkyl, C 5 -Cio-cycloalkyl, C 5 -C 0 heterocyclyl, C 5 -C 4 -aryl and C 5 -C 4 -heteroaryl or R 2 and R 3 together with the carbon atom to which they are attached form a five to fourteen-membered unsubstituted or at least monosubstituted ring system, the substituents being selected from among A group consisting of F, Cl, Br, OH, OR 9 , CN, N (R 9 ) 2 , COOH, COOR 9 , C (O) NH 2 , C (O) NHR 9 , C (O) N (R 9 ) 2, d-do-alkyl, C 5 -C 10 cycloalkyl, C 5 -C 10 heterocycly
  • R 9 is selected from C 1 -C 6 alkyl and C 5 -C 10 aryl
  • R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen, unsubstituted or at least monosubstituted C to C 10 -alkyl, wherein the substituents are selected from the group consisting of F, Cl, Br, OH and CN; is an integer in the range of 1 to 10; by homogeneous-catalyzed alcoholamination of alcohols of the general formula (Ii)
  • the hydroxyl groups (-OH) of the alcohol (II) used are reacted with the amino group (-NH-) of the piperazine (III) to give a mono-N-substituted-piperazine (I).
  • Each reacted hydroxyl group (-OH) produces a molecule of water
  • a process for homogeneous-catalyzed mecanical is disclosed for example in WO 2014/023549.
  • alcohols are reacted with primary or secondary monoamines.
  • the reaction of compounds containing two secondary amino groups is not described in WO 2014/023549.
  • Piperazine thus has two secondary amino groups (-NH-).
  • -NH- mono-N-substituted-piperazines
  • mono-N-substituted-piperazines (I) are accessible, the di-N-substituted-piperazines are obtained only in small amounts as a by-product.
  • alcohols (II) and piperazine (III) are used as starting materials.
  • Suitable alcohols (II) are compounds which contain at least one hydroxyl group (hereinafter also referred to as OH group).
  • the OH group may be present in the form of a primary alcohol group (-CH 2 -OH) or in the form of a secondary alcohol group (> CH-OH).
  • Suitable alcohols (II) are virtually all known alcohols which fulfill the abovementioned requirements.
  • the alcohols can be straight-chain, branched or cyclic.
  • the alcohols may also bear substituents which are inert under the alcohol alcoholation reaction conditions, for example, alkyloxy, alkenyloxy, dialkylamino and halogens (F, Cl, Br, I).
  • Alcohols (II) used are preferably monoalcohols, diols, triols or polyols.
  • Mono alcohols have an OH group.
  • Diols have two OH groups.
  • Triols have three OH groups.
  • Polyols have more than three OH groups.
  • Suitable alcohols (II) are, for example, those of the general formula (II): ROH
  • R 2 and R 3 are independently selected from the group consisting of hydrogen, unsubstituted or at least monosubstituted
  • R 9 is selected from C "-C -C 10 alkyl and C 5 -C 10 aryl;
  • R 4 , R 5 , R 6 , R 7 and R 8 are independently hydrogen, unsubstituted or at least monosubstituted C to C 10 alkyl, wherein
  • the substituents are selected from the group consisting of F, Cl, Br, OH and CN, an integer in the range of 1 to 10.
  • the ring system is preferably selected from the group consisting of unsubstituted or at least monosubstituted C 5 -C 10 -cycloalkyl and C 5 - C 10 heterocyclyl, where the substituents have the meanings given above.
  • Particularly preferred ring systems are selected from the group consisting of unsubstituted or at least monosubstituted cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Preferred alcohols (II) are, for example, those of the general formula (II):
  • R 2 is hydrogen
  • R 3 is selected from the group consisting of hydrogen, unsubstituted C 1 -C 30 -alkyl, C 5 -C 10 -cycloalkyl, C 5 -C 10 -heterocyclyl, C 5 -C 4 -aryl and C 5 -C 4 -heteroaryl ;
  • R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen; is an integer in the range of 1 to 10.
  • the subject of the present invention is thus also a method in which
  • R 2 is hydrogen
  • R 3 is selected from the group consisting of hydrogen, unsubstituted C 1 -C 30 -alkyl, C 5 -C 10 -cycloalkyl, C 5 -C 10 -heterocyclyl, C 5 -C 14 -aryl and C 5 -C 14 -heteroaryl
  • R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen
  • n is an integer in the range of 1 to 10.
  • Particularly preferred alcohols (II) are, for example, those of the general formula (II):
  • R 3 is selected from the group consisting of hydrogen and unsubstituted CiC 3 -alkyl, preferably hydrogen and C 1 -C 10 - alkyl, particularly preferably from hydrogen and C-
  • R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen; an integer in the range of 1 to 5, preferably 1 to
  • the subject of the present invention is thus also a method in which
  • R 2 is hydrogen
  • R 3 is selected from the group consisting of hydrogen and unsubstituted CiC 3 -alkyl, preferably from hydrogen and C1-C1 0 - alkyl, particularly preferably from hydrogen and C-
  • R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen; n is an integer in the range of 1 to 5, preferably 1 to 3.
  • the symbol " * " in the formulas (Ia) and (Ib) denotes the linking of the formulas (Ia) and (Ib) to the OH group of the alcohol (II). Accordingly, the symbol “ * " in the formulas (Ia ) and (Ib) the linking of the formulas (Ia) and (Ib) to the nitrogen atom of the mono-N-substituted-piperazine (I).
  • Suitable examples are the following monoalcohols: methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-butan-1-ol , 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, ethanolamine (monoethanolamine), 2-ethylhexanol, cyclohexanol, benzyl alcohol, 2-phenylethanol, 2- (p-methoxyphenyl) ethanol, furfuryl alcohol, 2 - (3,4-dimethoxyphenyl) ethanol, hydroxymethylfurfural, lactic acid, serine and fatty alcohols such as 1-heptanol (eananthalcohol; C 7 H 16 O), 1-octanol (capryl alcohol; C 8 H 18 0), 1-nonanol (pel
  • Preferred monoalcohols are selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-butane-1 -ol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, ethanolamine, 1-heptanol (eananthalcohol; C 7 H 16 O), 1-octanol (capryl alcohol; C 8 H 18 O), 1 Nonanol (pelargonyl alcohol, C 9 H 20 O), 1-decanol (capric alcohol, C 10 H 22 O), 1-undecanol (CnH 24 O), 10-undecen-1-ol (Cn H 22 O), 1 - Dodecanol (lauryl alcohol, C 12 H 26 O), 1-tridecanol (C 13 H 28 O), 1-te
  • the abovementioned fatty alcohols include both the pure compounds and mixtures of isomers of the primary fatty alcohols.
  • Particularly preferred monoalcohols are selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- Butan-1-ol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol.
  • Particularly preferred monoalcohols are selected from the group consisting of methanol and ethanol.
  • diols which can be used as starting materials in the process according to the invention are 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9- Nonanediol, 9-cis-octadecene-1, 12-diol (ricinoleic alcohol, C 18 H 36 O 2 ), 2,4-dimethyl-2,5-hexanediol, neopentyl glycol hydroxypivalate, 1, 4-bis (2-hydroxyethyl ) piperazine, diisopropanolamine, N-butyldiethanolamine, 1, 10-decanediol, 1, 12-dodecanediol, 2,5-bis (hydroxymethyl) furan, 1,4-bis (hydroxymethyl) cyclohexane monoethylene glycol (ethane-1, 2- dio
  • the present invention thus also provides a process in which the alcohol (II) is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methylbutan-1-ol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, monoethylene glycol (ethane-1,2-diol), diethylene glycol (2 - (2-hydroxyethoxy) ethane-1-ol) and triethylene glycol (2- [2- (2-hydroxyethoxy) ethoxy] ethane-1-ol.
  • the alcohol (II) is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, 1-pentanol,
  • the present invention thus also provides a process in which the alcohol (II) is selected from the group consisting of methanol, ethanol, n-propanol, n-butanol, isobutanol, 1-pentanol, 2-methylbutane 1 -ol, 2,2-dimethyl-1-propanol, monoethylene glycol (ethane-1, 2-diol), diethylene glycol (2- (2-hydroxyethoxy) ethane-1-ol) and triethylene glycol (2- [2- (2 -Hydroxyethoxy) ethoxy] ethan-1-ol.
  • the alcohol (II) is selected from the group consisting of methanol, ethanol, n-propanol, n-butanol, isobutanol, 1-pentanol, 2-methylbutane 1 -ol, 2,2-dimethyl-1-propanol, monoethylene glycol (ethane-1, 2-diol), diethylene glycol (2
  • triols or polyols which have at least one functional group of the formula (-CH 2 -OH) or (> CH-OH).
  • triols or polyols which can be used as starting materials in the process according to the invention are glycerol, trimethylolpropane, triisopropanolamine, triethanolamine, polyvinyl alcohol, polyalkylene glycols whose OH groups can be either primary and / or secondary alcohols, 2,2-bis ( hydroxymethyl) -1,3-propanediol (pentaerythritol), sorbitol, inositol, carbohydrates, sugars, sugar alcohols and polymers: such as glucose, mannose, fructose, ribose, deoxyribose, galactose, N-acetyl-glucosamine, fucose, rhamnose, sucrose , Lactose, cellobiose, maltose and
  • alcohols (II) monoalcohols and diols are preferred.
  • the alcohols (II) are selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, 1-pentanol, 2-pentanol, 3-pentanol, 2 -Methylbutan-1-ol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, monoethylene glycol (ethane-1, 2-diol), diethylene glycol (2- (2-hydroxyethoxy) ethane-1 -ol) and triethylene glycol (2- [2- (2-hydroxyethoxy) ethoxy] ethane-1-ol.
  • mono-N-substituted-piperazines (I) are selected from the group consisting of 1-methylpiperazine (CAS 109-01 -3), 1-ethylpiperazine (CAS 5308-25-8), 1-propylpiperazine (CAS 21867-64-1), 1- (1-methylethyl) piperazine (CAS 4318-42-7), 1-butylpiperazine (CAS 5610-49-1), 1 - (1-methylpropyl) -piperazine (CAS 34581 -21 -O), 1- (2-methylpropyl) -piperazine (CAS 5308-28-1), 1-pentylpiperazine (CAS 50866-75-6), 1 - ( 1-methylbutyl) -piperazine (CAS 82499-96-5), 1- (1-ethylpropyl) -piperazine (CAS 373356-51-5), 1- (2-methylbutyl) -piperazine (CAS 82499-96-5), 1- (1-ethylpropyl) -piperazine (
  • the alcohols (II) are selected from the group consisting of methanol, ethanol, n-propanol, n-butanol, isobutanol, 1-pentanol, 2-methylbutan-1-ol, 2,2 Dimethyl-1-propanol, monoethylene glycol (ethane-1, 2-diol), diethylene glycol (2- (2-hydroxyethoxy) ethane-1-ol) and triethylene glycol (2- [2- (2-hydroxyethoxy) ethoxy] ethane 1 -ol.
  • mono-N-substituted-piperazines (I) are selected from the group consisting of 1-methylpiperazine (CAS 109-01-3), 1-ethylpiperazine ( CAS 5308-25-8), 1-propylpiperazine (CAS 21867-64-1), 1-butylpiperazine (CAS 5610-49-1), 1 - (2-methylpropyl) -piperazine (CAS 5308-28-1), 1-pentylpiperazine (CAS 50866-75-6), 1- (2-methylbutyl) -piperazine (CAS 82499-91 -0), 1 - (1 , 2-dimethylpropyl) -piperazine (CAS 57184-42-6), 1-piperazineethanol (CAS 103-76-4), 2- [2- (1-piperazinyl) -ethoxy] -ethanol (CAS 13349-82-1 ), 2- [2- [2- [2- (1-piperazinyl) ethoxy]
  • the alcohols (II) are selected from the group consisting of methanol, ethanol, monoethylene glycol and diethylene glycol.
  • mono-N-substituted-piperazines (II) are selected from the group consisting of 1-methylpiperazine (CAS 109-01-3), 1-ethylpiperazine (CAS 5308-25-8), 1-piperazineethanol (CAS 103-76-4), 2- [2- (1-piperazinyl) -ethoxy] -ethanol (CAS 13349-82-1).
  • complex catalyst (IV) according to the invention is understood to mean both exactly one complex catalyst (IV) and mixtures of two or more complex catalysts (IV).
  • At least one complex catalyst (IV) which contains iridium as the metal component is used.
  • the inventive method is preferably carried out homogeneously catalyzed.
  • the complex catalyst (IV) contains a ligand of the general formula (V)
  • R 10, R 11, R 12, R 13, R 14 are independently hydrogen, methyl, ethyl, n-propyl, iso-propyl or phenyl.
  • the present invention thus also provides a process in which the complex catalyst (IV) contains a ligand of the general formula (V)
  • R 10 , R 11 , R 12 , R 13 , R 14 are independently hydrogen, methyl, ethyl, n-propyl, iso-propyl or phenyl.
  • complex catalysts (IV) which contain a ligand of the general formula (V) in which R 10 , R 11 , R 12 , R 13 and R 14 are methyl.
  • ligand (V) pentamethylcyclopentadienyl is thus particularly preferred.
  • Pentamethylcyclopentadienyl is also referred to as 1,2,3,4,5-pentamethylcyclopentadienyl and is hereinafter abbreviated to Cp * .
  • Cp * has the following formula
  • the present invention thus also provides a process in which the complex catalyst (IV) contains pentamethylcyclopentadienyl as ligands.
  • the ligand of the general formula (V), preferably the Cp * is coordinated to the iridium of the complex catalyst.
  • the complex catalyst (IV) used in the process according to the invention preferably contains iridium in the oxidation state +3 before the reaction starts. In general, the iridium in the complex catalyst (IV) has 4 coordination sites. It is presumed that the complex catalyst (IV), (V) is also present in the oxidation state +3 during the reaction.
  • the ligand of the general formula (V), preferably the Cp * occupies a coordination site of the iridium.
  • the remaining coordination sites, generally three, may be occupied by any other ligands.
  • the present invention thus also provides a process in which the complex catalyst (IV) contains iridium in the oxidation state +3.
  • Suitable complex catalysts (IV) are for example selected from the group consisting of [Cp * IrCI 2 ] 2 (CAS number: 12354-84-6), [Cp * IrBr 2 ] 2 (CAS number: 55971-89-6) , [Cp * Ir II 2 ] 2 (CAS number: 33040-12-9) [Cp * Ir (NH 3 ) 3 Cl 2 )] (CAS number: 1254038-09-9), [Cp * Ir (C 5 H 9 N 2 O) CI] (CAS number: 1098212-45-3), [Cp * Ir (C 5 H 9 N 2 O) Cl] (CAS number: 202662-76-8), chloro ( pentamethylcyclopentadienyl) ⁇ 5-cyano-2- ⁇ 1 - [(4-methoxyphenyl) imino-kN] ethyl
  • R 21 and R 22 are independently hydrogen, unsubstituted or at least mono-substituted Ci-Ci 0 alkyl, C 5 -C 10 cycloalkyl, C 5 -C 10 heterocyclyl, C 5 -C 10 aryl or C 5 -C 10 - Heteroaryl are or
  • R 21 and R 22 together with the atoms to which they are attached form an unsubstituted or at least monosubstituted five to ten membered ring system, the substituents being selected from the group consisting of NR 28 R 29 , OR 30 , SR 31 , C (0 ) OR 32 , C (O) NR 33 R 34 , N HC (NH 2 ) 2 + and unsubstituted or at least monosubstituted C 5 -C 10 aryl and C 5 -C 10 heteroaryl, wherein the substituents are selected from OH and NH 2 ;
  • X is fluoride, chloride, bromide or iodide
  • R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogen, methyl, ethyl, n-propyl, iso-propyl or phenyl;
  • R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 are independently hydrogen or CC 6 alkyl.
  • the present invention thus also provides a process in which the complex catalyst (IV) is selected from the group consisting of [Cp * IrCI 2 ] 2 (CAS number: 12354-84-6), [Cp * IrBr 2 ] 2 (CAS number: 55971-89-6), [Cp * lrl 2 ] 2 (CAS number: 33040-12-9) [Cp * lr (NH 3 ) 3 Cl 2 )] (CAS number: 1254038- 09-9), [Cp * Ir (C 5 H 9 N 2 O) Cl] (CAS number: 1098212-45-3), [Cp * Ir (C 5 H 9 N 2 O) Cl] (CAS- Number: 202662-76-8), chloro (pentamethylcyclopentadienyl) ⁇ 5-cyano-2- ⁇ 1 - [(4-methoxyphenyl) imino-kN] ethyl ⁇ phenyl-kC ⁇ iridium (III) (CAS number: 1258964-
  • R 21 and R 22 are independently hydrogen, unsubstituted or at least mono-substituted Ci-Ci 0 alkyl, C 5 -C 10 cycloalkyl, C 5 -C 10 heterocyclyl, C 5 -C 10 aryl, or C 5 -C 10 heteroaryl are,
  • R 21 and R 22 together with the atoms to which they are attached form an unsubstituted or at least monosubstituted five to ten membered ring system, the substituents being selected from the group consisting of NR 28 R 29 , OR 30 , SR 31 , C (0 ) OR 32 , C (O) NR 33 R 34 , NHC (NH 2 ) 2 + and unsubstituted or at least monosubstituted C 5 -C 10 aryl and C 5 -C 10 heteroaryl, wherein the substituents are selected from OH and NH 2 ;
  • X is fluoride, chloride, bromide or iodide
  • R 10 , R 11 , R 12 , R 13 and R 14 are independently hydrogen, methyl, ethyl, n-propyl, iso-propyl or phenyl;
  • R 28 , R 29 , R 30 , R 31 , R 32 , R 33 and R 34 are independently hydrogen or CC 6 alkyl.
  • the present invention thus also provides a process in which the complex catalyst (IV) is selected from the group consisting of [Cp * IrCI 2 ] 2 (CAS number: 12354-84-6), [Cp * Ir 2 ] 2 (CAS number: 33040-12-9) [Cp * Ir (NH 3 ) 3 Cl 2 )] (CAS number: 55971-89-6), [Cp * Ir (C 5 H 9 N 2 O) Cl ] (CAS number: 1098212-45-3), [Cp * Ir (C 5 H 9 N 2 O) Cl] (CAS number: 202662-76-8), chloro (pentamethylcyclopentadienyl) ⁇ 5-cyano -2- ⁇ 1 - [(4-methoxyphenyl) imino-kN] ethyl ⁇ phenyl-kC ⁇ iridium (l ll) (CAS number: 1258964-46-3), [Cp * Ir (P (CH 3) 3 ) CI 2 ] (
  • the complex catalyst (IV) may be neutral, single or double positively charged. Preferably, the complex catalyst (IV) is neutral.
  • the substituent NHC (NH 2 ) 2 + herein represents a substituent of the structural formula below, wherein the substituent is bonded via the dashed bond.
  • complex catalysts of the general formula (IVa) preferred are those in which R 10 , R 11 , R 12 , R 15 and R 14 are methyl and X is chloride.
  • the complex catalyst of the general formula (IVa) has a stereogenic center on the iridium central atom.
  • the general formula (IVa) includes according to the invention all stereoisomers (represented by wavy bonds in formula (IVa)) and is not limited to the configuration shown in formula (IVa).
  • the formula (IVa) thus also includes the stereoisomers (IVaa) and (IVbb).
  • the complex catalyst (IVa) also comprises all stereoisomers.
  • the complex catalyst (IV) also includes derivatives obtainable from the complex catalyst by protonation or deprotonation.
  • the preparation of complex catalysts of the general formula (IVa) is described in WO 2014/023549, to which reference is hereby made.
  • amino acids are ⁇ -amino acids.
  • the amino acids can be used both as L-a-amino acid and as D-a-amino acid.
  • D-L-o amino acids it is possible to use mixtures of the aforementioned configuration isomers, so-called D-L-o amino acids.
  • amino acids both naturally occurring amino acids and exclusively synthetically accessible amino acids can be used.
  • Preferred amino acids are selected from the group consisting of alanine, valine, leucine, iso-leucine, proline, tryptophan, phenylalanine, methonine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartate, glutamate, lysine, arginine, histidine , Citrulline, homocysteine, homoserine, (4R) -4-hydroxy-proline, (5R) -5-hydroxy-lysine, ornithine and sarcosine.
  • the abovementioned amino acids can be used both as L- ⁇ -amino acids and as D- ⁇ -amino acids. In addition, it is also possible to use mixtures of L- ⁇ - and D- ⁇ -amino acids of the abovementioned amino acids
  • Particularly preferred amino acids are selected from the group consisting of glycine, valine, proline and sarcosine. Particularly preferred amino acids are selected from the group consisting of glycine and proline.
  • the above comments and preferences for the amino acids apply to the complex catalyst (IVa) containing the amino acid, respectively.
  • the above statements and preferences for the amino acids also apply correspondingly.
  • Complex catalysts of the general formula (IVa) are thus those which are preferred, the iridium as metal component, Cp * (1, 2,3,4,5-pentamethylcyclopentadienylanion), chloride and an amino acid selected from the group consisting of alanine, valine, leucine, iso-leucine, proline, tryptophan, phenylalanine, methonine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartate, glutamate, lysine, arginine, histidine, citrulline, homocysteine, homoserine, (4R) -4-hydroxy Proline, (5R) -5-hydroxy-lysine, ornithine and sarcosine.
  • Cp * 1, 2,3,4,5-pentamethylcyclopentadienylanion
  • Complex catalysts of the general formula (IVa) are thus those which are preferred, the iridium as metal component, Cp * (1, 2,3,4,5-pentamethylcyclopentadienylanion), chloride and an amino acid selected from the group consisting of glycine, valine, proline and Containing sarcosine.
  • branched, unbranched, saturated and unsaturated groups are understood as meaning C 1 -C 3 -alkyl or C 1 -C 10 -alkyl or C 1 -C 6 -alkyl 1 to 6 carbon atoms..
  • alkyl groups having 1 to 4 carbon atoms More preferred are alkyl groups having 1 to 4 carbon atoms (C 1 -C 4 alkyl)
  • saturated alkyl groups are methyl, ethyl, n-propyl, isopropyl, n Butyl, isobutyl, sec-butyl, tert-butyl, amyl and hexyl.
  • unsaturated alkyl groups are vinyl, allyl, butenyl, ethynyl and propynyl.
  • the C 1 -C 30 -alkyl group or C 1 -C 10 -alkyl group or C 1 -C 6 -alkyl group may be unsubstituted or, with one or more substituents selected from the group consisting of F, Cl, Br, hydroxy (OH), C 1 -C 10 -alkoxy , C 5 -C 0 aryloxy, C 5 -C 0 -Alkylaryloxy, C 5 - C-io-heteroaryloxy containing at least one heteroatom selected from N, O, S, oxo, C 0 -C 3 cycloalkyl, phenyl, C 5 -C 0 heteroaryl containing at least one heteroatom selected from N, O, S, C 5 -C 10 heterocyclyl containing at least one heteroatom selected from N, O, S, naphthyl, amino, Ci-Ci 0 alkylamino, C5- C10-arylamino, Cs-C
  • C 5 -C 10 -cycloalkyl is understood here to mean saturated, unsaturated monocyclic and polycyclic groups.
  • Examples of C 5 -C 10 -cycloalkyl are cyclopentyl, cyclohexyl or cycloheptyl.
  • the cycloalkyl groups may be unsubstituted or substituted with one or more substituents as defined above for the C 1 -C 10 alkyl group.
  • C 5 -C 14 -aryl or C 5 -C 10 -aryl means an aromatic ring system having 5 to 14 or 5 to 10 carbons.
  • the aromatic ring system may be monocyclic or bicyclic.
  • Examples of aryl groups are phenyl, naphthyl, such as 1-naphthyl and 2-naphthyl.
  • the aryl group can be unsubstituted or substituted with one or more substituents as defined above under C 1 -C 10 -alkyl
  • C 5 -C 14 -heteroaryl or C 5 -C 10 -heteroaryl is used
  • a heteroaromatic system comprising at least one heteroatom selected from the group consisting of N, O and S.
  • heteroaryl groups may be monocyclic or bicyclic
  • the present invention also includes N-oxides of the nitrogen-containing heteroaryls
  • heteroaryls are thienyl, benzothienyl, 1-naphthothienyl, thianthrenyl, furyl, benzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, isoindolyl, indazolyl, purinyl, isoquinolinyl, quinolinyl, acridinyl, naphthyridinyl, quinoxalinyl , Quinazolinyl, cinnolinyl, piperidinyl, carbolinyl, thiazolyl, oxazolyl, isothiazolyl, isoxazo
  • C 5 -C 10 -heterocyclyl is understood as meaning five- to ten-membered ring systems which contain at least one heteroatom from the group consisting of N, O and S.
  • the ring systems can be monocyclic or bicyclic.
  • heterocyclic ring systems examples include piperidinyl, pyrrolidinyl, pyrrolinyl, pyrazolinyl, pyrazolidinyl, morpholinyl, thiomorpholinyl, pyranyl, thiopyranyl, piperazinyl, indolinyl, dihydrofuranyl, tetrahydrofuranyl, dihydrothiophenyl, tetrahydrothiophenyl, dihydropyranyl and tetrahydropyranyl.
  • the terms “reaction”, “process”, “reaction” and “alcohol amination” are used synonymously in the present case and have the same meaning content.
  • the complex catalyst (IV) according to the invention is preferably used directly in its active form.
  • the alcohol lamination is preferably carried out homogeneously catalysed in a liquid reaction medium, which is also referred to as a liquid phase.
  • the liquid reaction medium here includes all substances that are present in the Hyundaiamin réelle or formed in the Hyundaiamin réelle.
  • the liquid reaction medium thus generally comprises, depending on the progress of the reaction, the alcohol (II), piperazine (III), the complex catalyst (IV) and the mono-N-substituted-piperazine (I), and optionally a solvent.
  • the liquid reaction medium may be single-phase or multi-phase, for example two-phase, during the alcohol lamination.
  • the liquid reaction medium is preferably present in single phase during the alcohol lamination.
  • homogeneous catalysis is understood to mean that the catalytically active part of the complex catalyst (IV) is at least partially dissolved in the liquid reaction medium.
  • at least 90% of the complex catalyst (IV) used in the process is dissolved in the liquid reaction medium, more preferably at least 95%, most preferably more than 99%, most preferably the complex catalyst (IV) is completely dissolved in the liquid reaction medium (100%), in each case based on the total amount in the liquid reaction medium.
  • the complex catalyst (IV) is used in amounts (based on the iridium contained in the complex catalyst (IV)) in the range of 0.1 to 20 mol%, preferably in the range of 0.2 to 10 mol% and particularly preferably in the range of 0.5 to 6 mol% per mole of piperazine (II I) used.
  • the present invention thus also provides a process in which the complex catalyst (IV) in amounts, based on the iridium contained in the complex catalyst (IV), in the range of 0.1 to 20 mol% per mole of piperazine (I II) , is used.
  • the reaction generally takes place in the liquid phase at a temperature of 20 to 250 ° C.
  • the process according to the invention is preferably carried out at temperatures in the range from 50 ° C. to 180 ° C., more preferably in the range from 50 to 150 ° C. and in particular in the range from 80 to 130 ° C.
  • the present invention thus also provides a process in which the alcohol lamination takes place in a liquid phase at a temperature in the range from 20 to 250 ° C.
  • the liquid phase can be formed from the educts, ie the alcohol (II) or the piperazine (II I) and / or a solvent.
  • the reaction can generally be carried out at a total pressure in the range of 1 to 100 bar absolute, which includes both the autogenous pressure of the alcohol (II), the piperazine (II I) and optionally the solvent at the reaction temperature as well as the pressure of a gas such Nitrogen, argon or hydrogen can be carried out.
  • the process according to the invention is preferably carried out absolutely at a total pressure in the range from 1 to 80 bar absolute, more preferably at a total pressure in the range from 1 to 30 bar.
  • the present invention thus also provides a process in which the alcohol lamination is carried out absolutely at a pressure in the range from 1 to 80 bar.
  • the process according to the invention is carried out in the absence of hydrogen.
  • the absence of hydrogen is understood according to the invention that the reaction no additional hydrogen is supplied.
  • traces of hydrogen supplied via other gases and traces of hydrogen formed in the reaction are considered to be in the absence of hydrogen according to the present invention.
  • the present invention thus also provides a process in which the alcohol lamination takes place in the absence of hydrogen.
  • the average reaction time is generally 15 minutes to 100 hours, preferably 5 hours to 30 hours.
  • the piperazine (II I) can be used in stoichiometric, substoichiometric or superstoichiometric amounts with respect to the alcohol (II).
  • the molar ratio of piperazine (II I) to alcohol (II) before Hyundaiamintechnik is generally in the range of 1 to 8 to 8 to 1, preferably in the range of 1 to 4 to 6 to 1, particularly preferably in the range of 1 to 1, 5 to 5 to 1 and in particular in the range of 1 to 1 to 4 to 1.
  • the piperazine (II I) is added to the alcohol (I I) in a molar ratio of 2 to 1 to 4 to 1.
  • piperazine (I II) is used in the ratio of 1 to 1 (stoichiometric) to 4 to 1 (more than stoichiometric), based on the number of OH groups in the alcohol (II).
  • the present invention thus also provides a process in which the molar ratio of piperazine (III) to alcohol (II) is in the range from 1: 8 to 8: 1.
  • the process according to the invention can be carried out both in the presence of a solvent and without solvent.
  • the process according to the invention is preferably carried out in the presence of a solvent.
  • Suitable solvents are polar and nonpolar solvents which can be used in pure form or in mixtures. For example, only a non-polar or only one polar solvent can be used in the process according to the invention.
  • nonpolar solvents examples include saturated and unsaturated hydrocarbons, such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene (o-xylene, m-xylene, p-xylene) and mesitylene, and linear and cyclic ethers, such as diethyl ether, 1 4-dioxane, THF (tetrahydrofuran), MTBE (tert-butyl methyl ether), diglyme and 1,2-dimethoxyethane.
  • toluene, xylenes, tetrahydrofuran or mesitylene Particularly preferred is toluene or tetrahydrofuran.
  • Suitable polar solvents are water, dimethylformamide, formamide, tert-amyl alcohol and acetonitrile. Preferably, water is used. Water can be added both prior to the reaction, formed in the reaction as water of reaction or added after the reaction in addition to the water of reaction.
  • bases can have a positive effect on product formation.
  • Suitable bases include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal carbonates, alkaline earth carbonates, alkali metal bicarbonates and alkaline earth hydrogen carbonates, of which 0.01 to 100 molar equivalents can be used with respect to the molar amount of iridium contained in the complex catalyst (IV). If the complex catalyst (IV) is used as dimer, the addition of the abovementioned bases in the process according to the invention is preferred. Most preferably, then, an alkali metal alcoholate is added as a base, with potassium tert-butoxide being most preferred.
  • the process according to the invention is preferably carried out without the addition of the abovementioned bases.
  • the piperazine (III), the alcohol (II), preferably together with a solvent, and the complex catalyst (IV) are introduced into a reactor.
  • the supply of the piperazine (III), the alcohol (II), optionally the solvent and the complex catalyst (IV) can be carried out simultaneously or separately.
  • the reaction can be carried out continuously, in semibatch mode, in batch mode, back mixed in product as a solvent or not mixed back in straight pass.
  • a primary or secondary hydroxyl group of the alcohol (II) is reacted with the amino group (-NH-) of the piperazine (III) to form a mono-N-substituted-piperazine (I), wherein each reacted one mole of water of reaction per mole Amino group (-NH-) of piperazine forms.
  • the reaction product formed in the reaction generally contains the corresponding mono-N-substituted-piperazine (I), optionally the solvent, the complex catalyst (IV), optionally unreacted starting materials (alcohol (II) or piperazine (III)) and the resulting reaction water.
  • the present invention will be clarified by the following examples without, however, limiting to them. The determination of the conversions and selectivities took place by means of gas chromatography. Gas chromatographic measurements were performed on an Agilent 6890N modular GC equipped with a split-mode capillary injection system and a flame ionization detector (FI D).
  • the capillary column used was a DB-1 column (Agilent 122-1033, 30 m ⁇ 0.25 mm ⁇ 1.00 ⁇ m, helium flow 1, 0 mL / min, temperature program: 70 ° C. for 5 min, ramp with temperature increase 5 ° C / min to 300 ° C, 300 ° C for 10 min).

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Abstract

Procédé de production de pipérazines mono-N-substituées représentées par la formule générale (I) par amination à catalyse homogène d'alcools représentés par la formule générale (II) avec la pipérazine (III) en présence d'un catalyseur complexe (IV) qui renferme de l'iridium.
PCT/EP2017/050824 2016-01-20 2017-01-16 Procédé de production à catalyse homogène de pipérazines mono-n-substituées Ceased WO2017125358A1 (fr)

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US20190308930A1 (en) * 2016-12-15 2019-10-10 Akzo Nobel Chemicals International B.V. Process for manufacturing ethylene amines
CN112107967A (zh) * 2020-09-28 2020-12-22 绍兴兴欣新材料股份有限公司 一种有机胺脱硫溶液及其生产方法和应用
US10995058B2 (en) 2016-12-15 2021-05-04 Nouryon Chemicals International B.V. Process for manufacturing hydroxyethyl ethylene amines

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190308930A1 (en) * 2016-12-15 2019-10-10 Akzo Nobel Chemicals International B.V. Process for manufacturing ethylene amines
US10975017B2 (en) * 2016-12-15 2021-04-13 Nouryon Chemicals International B.V. Process for manufacturing ethylene amines
US10995058B2 (en) 2016-12-15 2021-05-04 Nouryon Chemicals International B.V. Process for manufacturing hydroxyethyl ethylene amines
CN112107967A (zh) * 2020-09-28 2020-12-22 绍兴兴欣新材料股份有限公司 一种有机胺脱硫溶液及其生产方法和应用

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